Chemical Sensor Dan FIA

Chemical Sensors dan Flow
Injection Analysis (FIA)

Ion Selective Electrodes
Potentiometric sensors
A large subset of electrochemical sensors
Principle: electric potential develops at the surface of
a solid material immersed in solution containing ions
that exchange at the surface.
The potential is proportional to the number or
density of ions in the solution.
A potential difference between the surface of the
solid and the solution occurs because of charge
separation at the surface.
The contact potential, analogous to that used to set up a
voltaic cell cannot be measured directly.
If a second electrode is provided, an electrochemical cell is
setup and the potential across the two electrodes is directly
measurable.
To ensure that the potential is measured accurately, and
therefore that the ion concentration is properly represented
by the potential, it is critical that the current drawn by the
measuring instrument is as small as possible (any current is a
load on the cell and therefore reduces the measured
potential).
For a sensor of this type to be useful, the potential
generated must be ion specific that is, the
electrodes must be able to distinguish between
solutions.
These are called ion-specific electrodes or
membranes.
The four types of membranes are:
Glass membranes, selective for H
+
, Na
+
and NH
4
+
and
similar ions.
Polymer-immobilized membranes: In this type of membrane,
an ion-selective agent is immobilized (trapped) in a polymer
matrix. A typical polymer is PVC
Gel-immobilized enzyme membranes: the surface reaction is
between an ion specific enzyme which in turn is either
bonded onto a solid surface or immobilized into a matrix -
mostly for biomedical applications
Soluble inorganic salt membranes: either crystalline or
powdered salts pressed into a solid are used. Typical salts are
LaF
3
or mixtures of salt such as Ag
2
S and AgCl. These
electrodes are selective to F
, S
2
and Cl
and similar ions.

Classification of ion-selective electrodes

A: Fundamental ISEs
A.1. Solid-state membrane (Glass & precipitate)
A.2. Liquid membrane
A.2.1. Ion-exchanger based
A.2.2. Ionophore based

B. Sensitized ISEs
B.1. Gas sensing probes
B.1.1. Permeable membrane covered
B.1.1.1. Differential gas sensors
B.1.2. Air-gap separated

B.2. Enzyme modified ISEs
Glass membrane sensors
By far the oldest of the ion-selective electrodes,
Used for pH sensing from the mid-1930s and is as
common as ever.
The electrode is a glass made with the addition of
sodium (Na
2
O) and aluminum oxide (Al
2
O
3
),
Made into a very thin tube-like membrane.
This results in a high resistance membrane which
nevertheless allows transfer of ions across it.
The basic method of pH sensing is shown in Figure
8.7a.
pH sensor
pH sensor
Consists of the glass membrane electrode on the left and a
reference electrode on the right.
The reference electrode is typically an Ag/AgCl electrode in
a KCl aqueous solution or a saturated Calomel electrode
(Hg/Hg
2
Cl
2
in a KCl solution).
The reference electrode is normally incorporated into the
test electrode so that the user only has to deal with a
single probe as shown in Figure 8.7b.
The sensor is used by first immersing the electrode into a
conditioning solution of Hcl (0.1.mol/liter) and then
immersing it into the solution to be tested. The electric
output is calibrated in pH.
A sensor of this type responds to pH from 1 to 14.
pH probe with reference electrode
Glass membrane sensors
Modifications of the basic configuration, both in
terms of the reference electrode (filling) as well as
the constituents of the glass membrane lead to
sensitivity to other types of ions as well as to sensors
capable of sensing dissolved gas in solutions,
particularly ammonia but also CO
2
, SO
2
, HF, H
2
S and
HCN

Soluble inorganic salt membrane
sensors
Based on soluble inorganic salts which undergo ion-
exchange interaction in water and generate the
required potential at the interface.
Typical salts are the lanthanum fluoride (LaF
3
) and
silver sulfide (Ag
2
S).
The membrane may be either
a singe crystal membrane,
a sintered disk made of powdered salt
a polymer matrix embedding the powdered salt
each has its own application and properties
sensors
The structure of a commercial sensor used to sense
fluoride concentration in water is shown next
The sensing membrane, made in the form of a thin
disk grown as a single crystal.
The reference electrode is created in the internal
solution (in the case: NaF/NaCl at 0.1 mol/liter).
The sensor shown can detect concentrations of
fluoride in water between 0.1 and 2000 mg/l.
This sensor is commonly used to monitor fluoride in
drinking water (about 1mg/l).
sensors for fluoride
sensors
Membranes may be made of other materials such as
silver sulfide.
The latter is easily made into thin sintered disks from
powdered material and may be used in lieu of the
single crystal.
Other compounds may be added to affect the
properties of the membrane and hence sensitivities
to other ions.
This leads to selective sensors sensitive to ions of
chlorine, cadmium, lead and copper and are often
used to sense for dissolved heavy metals in water.
Polymeric salt membranes
Polymeric membranes are made by use of a
polymeric binder for the powdered salt
About 50% salt and 50% binding material.
The common binding materials are PVC,
polyethylene and silicon rubber.
In terms of performance these membranes
are quite similar to sintered disks.

Polymer-immobilized ionophore
membranes
A development of the inorganic salt membrane
Ion-selective, organic reagents are used in the
production of the polymer by including them in the
plasticizers, particularly for PVC.
A reagent, called ionophore (or ion-exchanger) is
dissolved in the plasticizer (about 1% of the
plasticizer).
This produces a polymer film which can then be used
as the membrane replacing the crystal or disk in
sensors.
membranes
The construction of the
sensor is simple
Shown in Figure 8.9 and
includes an Ag/AgCl
reference electrode.
The resulting sensor is a
fairly high resistance sensor.

membranes
A different approach to building
polymer-immobilized ionophore
membranes is shown in Figure 8.10.
It is made of an inner platinum wire on
which the polymer membrane is coated
The wire is protected with a coating of
paraffin.
This is called a coated wire electrode.
To be useful a reference membrane
must be added.
Membrane Solution
Cation (p)
Anion
(Permselective)
Cation (i)
(ionselective)
Regulated by the
selectivity coefficient
R
-
(TTFMPB)
M
+
N
+
M
+
time
i
0

i
M
+
Current
density
i
M
+
Q
Ion-exchanger
based membranes
CF
3
CF
3
B
CF
3
CF
3
CF
3
CF
3
CF
3
CF
3
tetrakis[3,5-
bis(trifluoromethyl)phenyl]borat
e (TTFMPB)

( )
+
+
aq
N
- +
org
N
k =
R N
(

(
(

( )
+
+
aq
M
- +
org
M
k =
R M
(

(
(

i
0

i
N
+
i
N
+
Dissociated cation exchanger

R
+
>Cs
+
>Rb
+
> K
+
>Na
+
>Li
+

Dissociated anion exchanger:

ClO
4
-
> SCN
-
> I
-
> Sal
-
> NO
3
-
> Br
-
> Cl
-
> HCO
3
-
> OAc
-
> SO
4
-
>HPO
4
2-

B

-
K
+
N

+
( ) ( )
( )
( )
( ) ( )
+
+
+ +
- + +
aq
org
- + + - + + M
aq aq ionexch.
org org
- + +
N
aq
org
+ +
aq aq
M N
- + - +
org org
R N M
k
R M +N = R N +M K = =
k
R M N
M N
k = k =
R M R N
(
(

(

(
(

(

( (

( (
( (

CF
3
CF
3
B
CF
3
CF
3
CF
3
CF
3
CF
3
CF
3
Hofmeister selectivity sequence
Membrane Solution
Cation (p)
Anion
Cation (i)
Regulated by the
R
-
M
+
N
+
B
M
+
) a K a ln(
F z
RT
E E
i
p
z
z
i
pot
i , p p
p
0
p
+ + =
( ) ( )
( )
( )
( ) ( )
+
+
+ +
- + +
aq
org
- + + - + + M
aq aq ionexch.
org org
- + +
N
aq
org
+ +
aq aq
M N
- + - +
org org
R N M
k
R M +N = R N +M K = =
k
R M N
M N
k = k =
R M R N
(
(

(

(
(

(

( (

( (
( (

logK
M
+
,N
+

pot
logK

ionexch
.
-4 -2 0 2 4
4
2
0
-2
-4
Li
+
Na
+
K
+
(CH
3
)
4
N
+
(C
2
H
5
)
4
N
+
Hofmeister selectivity sequence
Membrane Solution
Cation (p)
Anion
Cation (i)
Regulated by the
Ca
2+
Mg
2+
( )
| |
2
2
2
2
+
+
aq
Ca
org
org org org
org org
Ca
k =
CaDDP
Ca DDP CaDDP
CaDDP
K
Ca DDP
+
+
(

(

+ =
=
( (

( )
| |
2
2
2
2
+
+
aq
Mg
org
org org org
org org
Mg
k =
MgDDP
Mg DDP MgDDP
MgDDP
K
Mg DDP
+
+
(

(

+ =
=
( (

Deviations from
Hofmeister selectivity
sequence

ASSOCIATION WITH
THE ION-
EXCHANGER
O
P
O
O
O
Ionophore / ion-exchanger
Ca-DDP
O
P
O
O
DOPP
Plasticizer for Ca
selectivity
complete
association (org)
Decanol
OH
Plasticizer for divalent (Ca
2+
+Mg
2+
)
selectivity complete dissociation
pot -4 pot
Ca,Mg Ca,Mg
K 10 (DOPP) K 1 (Decanol)
aq
j pot JS
i, j
aq
i IS
k
K
K = f ;
k K
| |
|
\ .
Membrane Solution
Ionophore-Cation (p)
ionophore
+
Cation (p)
Cation (p)
Anion
Cation (i)
R
-
M
+
N
+
K
+

K
+

B
Regulated by the
Ionophore based, mobile site
ion-selective membrane:
PVC (33%) (PVC-COOH, PVC-OH, PVC-NH
2
, silicone rubber, poly-urethane,
methacrylate polymers)

Plasticizer (66%) (phtalate esters, sebacate esters,o-NPOE, adipic acid
esters)

1% Ionophore (chromoionophore)

50% (mol) Lipophilic ion additive
(NaTPB, KTpClPB,KTbTFMPB)

CF
3
CF
3
B
CF
3
CF
3
CF
3
CF
3
CF
3
CF
3
K
+
B
Na
+
B Cl
Cl
Cl
Cl
K
+
N
O N
O
N
CF
3
CF
3
B
CF
3
CF
3
CF
3
CF
3
CF
3
CF
3
K
+
PVC (33 %)

Plasticizer: DOS (66 %)

Ionophore (1%)

Lipophilic Anion (< 1% )
(10-90 mol % with respect of the ionophore)

O
O
O
O
H
+
selective chromoionophore ETH 5294
K
+
selective ionophore valinomycin
NO
2
O
Cl Cl Cl
n
Potential difference
A
-
Ionophore
complex
M
+
Primary cation
ionophore
Anion
R
-

Lipohylic
additive
200 m
M
+
M
+
M
+
M
+
M
+
M
+
A
-
A
-
A
-
A
-
A
-
M
+
A
-
A
-
A
-
A
-
A
-
R
-

R
-

R
-

R
-

N
+
N
+
N
+
N
+
N
+
N
+
N
+
Interfering cation
M
+
M
+
M
+
M
+
M
+
o
o
o
membrane
R
-
R
-
=
M
+
M
+
M
+
M
+
M
+
A
-
A
-
A
-
0
log
aq
org
a
S
a
c c = +
( )
( )
log
aq rigt
M right left
aq left
a
S
a
c c c = =
Potassium ionophores
Calcium ionophores
Hydrogen ionophores
Fig. 13.14. 14-Crown-4 ether that selectively binds lithium ion.
The crown ether cavity size is just right for complexing lithium ion.
It is placed in a PVC plastic membrane.
Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Fig. 13.15. Ionophores for H
+
, Na
+
, and Ca
2+
.
Amide-based ionophores in PVC membranes are good complexers of these ions.
Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Typical ISE Calibration Graph
NB: X-axis units are the logarithm of the Molar Activity of the Ion
New Hg
2+
-selective Chromo-
and Fluoroionophore Based upon
8-Hydroxyquinoline
So Yun Moon and Suk-Kyu Chang
Department of Chemistry
Chung-Ang University
Introduction
Binding Site
N
OH
N
B
N
F F
Signaling Unit
Selectivity :
Transition and
Heavy Metal
Ions
High Quantum Yield
Longer Wavelength
Narrow Absorption Band
New Ionophore Having
Hg
2+
-selective
Chromogenic and
Fluorogenic
Signaling Behavior
+
Synthesis of Ionophore 1
N CHO
OH
N
OH
N
B
N
F
F
i), ii), iii)
i) 2,4-Dimethylpyrrole, ii) chloranil, iii) NEt
3
, BF
3
-OEt
2
1
0
0.5
1
1.5
2
350 450 550 650
Wavelength (nm)
A
b
s
o
r
b
a
n
c
e
Cu
2+
Hg
2+
Zn
2+
Host only
UV Absorption Spectra of 1 in dioxane-
H
2
O (1 : 3, v/v) with various metal ions.
[1] = 1 x 10
-4
M, [M
2+
] = 1 x 10
-2
M
Color changes in 1 upon the
complexation with Hg
2+
ion.
[1] = 1 x 10
-4
M, [M
2+
] = 1 x 10
-2
M
No metal
ion

Hg
2+
Pb
2+
Hg
2+
-selective Chromogenic Behavior of 1
0
0.5
1
1.5
2
350 450 550 650
Wavelength (nm)
A
b
s
o
r
b
a
n
c
e
UV Absorption Spectra of 1 Upon Addition of
Increasing Amount of Hg
2+
in the Presence of
Physiological Background Metal Ions
Figure 3. UV Absorption Spectra of 1
in dioxane-H
2
O (1 : 3, v/v) . [1] = 1 x 10
-4
M,

Equiv.
0.0
0.5
1.0
2.0
3.0
4.0
5.0
50

Hg
2+
-selective Fluorogenic Behavior of 1

0
1
2
3
4
5
6
490 540 590 640
Wavelength (nm)
F
l
u
o
r
e
s
c
e
n
c
e

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Hg
2+
Cu
2+
1 only
Pb
2+
Zn
2+
, Ni
2+
No metal
ion

Hg
2+
Pb
2+
Fluorescence spectra of 1 in dioxane-
H
2
O (1 : 3, v/v) with various metal ions.
[1] = 5 x 10
-5
M, [M
2+
] = 5 x 10
-4
M
Fluorescent change of 1 upon the
complexation with Hg
2+
ion.
[1] = 5 x 10
-5
M, [M
2+
] = 5 x 10
-4
M
Fluorescence Spectra of 1 Upon Addition of Increasing
Amount of Hg
2+
in the Presence of Physiological
Background Metal Ions

0
2
4
6
8
490 540 590 640
Wavelength (nm)
F
l
u
o
r
e
s
c
e
n
c
e

I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Equiv.
0.0

0.2
5
0.5
0.6
0.7
1.0
1.2
2.0
5.0
50

100
Ion
mM
Na
138
Mg
1
Ca
3
K
4
Fe
0.02
Zn
0.02
Cu
0.015
Co
0.002
Ni
0
Metal Ions
in blood
Fluorescence Spectra of 1 in dioxane-H
2
O
(1 : 3, v/v) . [1] = 5 x 10
-5
M,

Conclusion
1. New Hg
2+
-selective

Fluorogenic sensor was synthesized by
conjugating 8-Hydroxyquinoline with BODIPY function.
2. Remarkable Hg
2+
-selective Fluorescence Quenching
(ON-OFF type switching effect).
3. Also exhibited a Hg
2+
-Selective Chromogenic Behavior:
No metal ions : Yellow, Hg
2+
: Red, Cu
2+
: Light Reddish
Yellow.
4. Selectivity : Hg
2+
>> Cu
2+
> Pb
2+
~Ni
2+
~ Zn
2+
~ Ca
2+
.
5. It can be used as a new ion sensor for the detection of toxic
Hg
2+
in a variety of chemical and biological systems.
Novel Hg
2+
-selective Pyrenylacetamide
Ionophore Derived from
p-tert-Butylcalix[4]arene-diaza-crown Ether
Ju Hee Kim and Suk-Kyu Chang
Chung-Ang University
Introduction
Fluorescence
-ON
Fluorescence-
OFF
Monomer Emission (< 20% Water)
Excimer Emission (~ 50% Water)
Excimer ON
Excimer OFF
Hg
2+
N
O
N
O
Pyrene Moiety
Hg
2+
Design and Synthesis of Ionophore from
p-tert-Butylcalix[4]arene-aza-crown Ether
K
2
CO
3
, KI, CH
3
CN
N
H
O
Cl
OH
O O
Bu
t
Bu
t
N N
HO
Bu
t
Bu
t
N
O
H
N
O
H
2 45%
OH
O O
Bu
t
Bu
t
NH HN
HO
Bu
t
Bu
t
1
0
1
2
3
4
5
6
7
350 400 450 500 550 600
Monomer and Excimer Fluorescence Spectra of
Calix-aza-crown Pyrenylacetamide 2
Monomer
Excimer
Fluorescence spectra of 2 in various solvent system.
[Ligand] = 1 x 10
-5
M, MeOH : H
2
O (v/v) = 8:2 (),
9:1 (), 10:0 (), 5:5 (), 4:6 (), 1:9 ().
F
l
u
o
r
e
s
c
e
n
c
e

i
n
t
e
n
s
i
t
y
(
a
.

u
.
)

Wavelenghth (nm)
0
1
2
3
4
5
6
7
8
0 20 40 60 80 100
Ratio of H
2
O (%)
The changes of intensity ratios
(I
474
/I
385
) as a function of H
2
O
composition.
Changes in Monomer Emission Intensity of 2
Mg
Ni
Hg
Cu
Co
Cd
Ca
Zn
100% MeOH
90% MeOH
80% MeOH
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
F
l
u
o
r
e
s
c
e
n
c
e

I
n
t
e
n
s
i
t
y

C
h
a
n
g
e
(

(
I
0
-
I
)
/
I
0
)

The effects of H
2
O/MeOH composition on the
selectivity toward representative transition and
heavy metal ions. [2] = 1 x 10
-5
M, [M
2+
] =1 x 10
-3
M
Fluorescence Titration of 2 with Hg
2+
Ions
in the Presence of Background Metal Ions
0
1
2
3
4
5
6
300 350 400 450 500 550
In MeOH/H
2
O (9 : 1, v/v) [2] = 1 x 10
-5
M : (-); 2 only, ();
2 in the presence of background metal ions ():3, (): 10,
():15, and (): 50 equiv of Hg
2+
ions.
F
l
u
o
r
e
s
c
e
n
c
e

i
n
t
e
n
s
i
t
y
(
a
.

u
.
)

Wavelength (nm)
Changes in Fluorescence Intensity of Excimer 2
with Various Metal Ions
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
zinc pb ni mg hg cu co cd ca ba F
l
u
o
r
e
s
c
e
n
c
e

I
n
t
e
n
s
i
t
y

C
h
a
n
g
e
(

(
I
0
-
I
)
/
I
0
)

In MeOH-H
2
O (5 : 5, v/v). [2] = 1 x 10
-5
M, [M
2+
]
=1 x 10
-3
M
Fluorescence Titration with Hg
2+
in Physiological
Metal Ions in Excimer Emission Region
0
1
2
3
4
5
6
350 400 450 500 550 600
Wavelength (nm)
F
l
u
o
r
e
s
c
e
n
c
e

i
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Fluorescence spectra of 2 in MeOH/H
2
O
(1 : 1, v/v) .
() : 2, () : 1, () : 5, () : 10, () : 30, () : 70,
and () : 200 equiv of Hg
2+
Ions.
Ion mM
Na 138
Mg 1
Ca 3
K 4
Fe 0.02
Zn 0.02
Cu 0.015
Co 0.002
Ni 0
Metals in Blood
Conclusion
1. Novel Hg
2+
-selective

chemosensor was synthesized by conjugating
Calix-aza-crown Ether with Pyrenylacetamide functions.
2. In 10% aq. MeOH solution: Hg
2+
-selective Monomer Emission
Quenching of Pyrene Moiety (ON-OFF).
3. In 50% aq. MeOH solution: Hg
2+
-selective Excimer Emission
Quenching (ON-OFF).
4. Selectivity : Hg
2+
>> Cu
2+
> Pb
2+
~ Zn
2+
~ Mg
+
~ Ca
2+
.
5. New ION SENSOR for the detection of toxic Hg
2+
Ions in a
variety of chemical and biological systems.
HPTS- Optical pH Sensor
pH sensitive
fluorescent dye
Absorbance /
Excitation changes with
pH
Emission at 520 nm
Excitation Ratiometric
pH SENSOR ASSEMBLY FOR
OPTICAL CHEMICAL SENSOR
White microfiltration membrane backing
PEG-dye copolymer hydrogel
Transfer adhesive
Note: All Optical Chemical Sensors Are Based on
Same Concept as pH Sensor
pH Sensor Calibration in Cell Suspension
0.0
0.5
1.0
1.5
2.0
2.5
3.0
6 6.5 7 7.5 8 8.5 9
clear buffer
e.coli/LB suspension
(OD
600nm
= 0.25)
I
n
t
e
n
s
i
t
y

R
a
t
i
o
pH
Optical Sensors
Fluorescent Biosensors
Total Internal Reflection
Surface Plasmon Resonance
Interferometry

Fluorescent biosensor design
Bissel et al. Topics in Current Chemistry, Vol. 168 , Springer Verlag (1993), pp. 223-261
The fundamental design of a fluorescent biosensor
consists of a receptor binding site and a fluorophore
connected by a linker.

The linker provides a means for triggering a change
in the fluorescence of the attached fluorophore.
Linker Fluorophore
Receptor/
Binder
Fluorescent biosensors
The principal of operation is that there must be a
fluorescent switch. The switch is triggered by
a binding event. The binding molecule can quench
fluorescence or cause a conformational change that
unquenches fluorescence. One of the most common
quenching mechanisms is electron transfer:
hv
DA D
1
A D
+
A
-
DA
+ hv
DA
In the scheme above the donor D acts as a
fluorescence quencher.
Energy diagram for a fluorescent sensor
D
1
A
Electron transfer quenching of a fluorescent
sensor
D
1
A
D
+

A
-

E
s

Fluorescent sensors
Cooper and James SPIE (1999), 3602, 194-201
Crown ethers bind sodium with good selectivity.
In the fluorescent molecule shown below the binding
of sodium results in fluorescence quenching.
Boronic ester-based biosensors:
The classical mechanism
Cooper and James SPIE (1999), 3602, 194-201
Formation of a boron-nitrogen bond can occur by
formation of boronic esters. This interaction dramatically
reduces fluorescence quenching by the amine nitrogen
lone pair. The result is a switch from a non-fluorescent
to fluorescent state upon binding to a saccharide.

B
N
PBE-OTMA
O
O
B
N
O
O
+
H
2
O
+
H
HO
_
PBA-OTMA
B
OH
OH
N
+
H
2
O
B
OH
OH
N
H
2
O
Hydrolysis Less Favored
Hydrolysis Strongly Favored
Novel mechanism for fluorescence triggering

In aprotic solvents (DMSO, CH
3
CN, CHCl
3
),
fluorescence of the ester is lower than that of the acid

0
50
100
150
200
250
300
350
400
380 400 420 440 460 480 500
nm
I
0 mM
5.71 mM
Fluorescence profile of acid in anhydrous DMSO decreased with the addition of cis-1, 2-
cyclopentane diol
N
B
OH
HO

Addition of water increase the fluorescence
intensity
H
+
N
B-
O
O
OH
DMSO and Water

A Hydrolysis Mechanism for Fluorescent State Switching
N
H
HO
+
N
B
OH
HO
B
O
O
Weakly fluorescent
light
Strongly fluorescent
Diol
(Saccharide)
-
Franzen, Ni and Wang J. Phys. Chem. 2003, 107, 12942
Implantable glucose sensor
Detector
Laser diode
Fluorescent
molecules
Power supply and transmitter
SMSI, Inc.
Detector
Laser diode
Fluorescent
molecules
SMSI, Inc.
Detector
Laser diode
Glucose quenches
fluorescence
SMSI, Inc.

Cell Surface Target Molecules
OH
O
O
O
O
O
O
O
NHAc
OH
Me
HO
OH
OH
CH
2
OH
Me
HO
OH
HO
OH
OH
OH
O
O
O
O
OH
O
NHAc
OH
Me
HO
OH
OH
OH
HO
OH
NHAc
OH
O
O
OH
O
O
OH
Me
HO
OH
O
OH
OH
HO
O
O
COOH
OH
AcNH
OH
OH
OH
NHAc
OH
O
O
OH
O
O
OH
OH HO
O
O
OH
Me
HO
OH
O
COOH
OH
AcNH
OH
OH
OH
Lewis Y tetrasaccharide
Lewis X trisaccharide
sialy Lewis X tetrasaccharide
sialy Lewis a tetrasaccharide

The Approach
OH
OH OH
OH
B
B
HO OH
HO OH
Carbohydrate
Receptor, nonfluorescent
or weakly fluorescent
O
O O
O
B
B
Carbohydrate-
receptor complex
Strongly fluorescent
- 2 H
2
O
Bidentate design

Computer-aided design can be used to generate
structures that have the appropriate geometry. A recent
example is shown above for sensing of pyranose.
He and Druekhammer, Angew. Chem. 2001, 40, 1714

Some Synthesized Diboronic Acids

12a
compounds
-(CH
2
)
10
-
12b
12c
O O
12d
12e
-(CH
2
)
3
-
12f
12h
-(CH
2
)
2
-
12i -(CH
2
)
6
-
12j -(CH
2
)
20
-
12k
12l
O
12m
-(CH
2
)
12
-
12n
12o
12p
-(CH
2
)
5
-
12q
12g
compounds
LINKER
LINKER
12r O
12s
12t
12u
12v
12w
12x
12y
12z
S
N
-(CH
2
)
14
-
-(CH
2
)
4
-
compounds LINKER
5 M Boronic Acid Targeting Molecule
Fluorescent Cell Targeting Assay
Sialyl Lewis X Sialyl Lewis Y Control

12q

12a

Synthesis Cation Sensing Material
0.05g, 0.32mmol
2.00g, PS latex
Ion exchange resin,
solvent
0.10g, 1.4mmol
Parafilm
spacer, 125
um
Quartz disk
1. CCA Self-assemble
diffraction film
2. PCCA
365 nm
90 min
3. Hydrolyzed
PCCA
0.15g, 0.64mmol
0.20g, 1.04mmol
Results and Discussion
Cu
2+
sensor
757 nm
Proposed Mechanism of Sensing Cu
2+

Cu
2+

Low concentration
- Cu
2+

+ Cu
2+

Cu(hydroxyquinolate)
2

Log (K
f
) = 21.87
Shrink blue shrift

bisligand
Cu(hydroxyquinolate)
Log (K
f
) = 10.70
Breaking crosslonk red shrift

monoligand
Formation of the liganded complexes
5-acetamido-8-hydroxyquinoline in acetate-buffered
saline
8-hydroxyquinoline-functionalized
CCA-free hydrogel

380
250-270
Other result: AA shows NO Cu
2+
is retained by PCCA w/o 8-
hydroxyquinoline
Diffraction wavelength vs. concentration
S = Cu
2+
mol
/ 2 ligand
mol

Outmost layer effect
1
M
5-acetamido-8-hydroxyquinoline

colloid-free 8-hydroxyquinoline-
containing hydrogel

Cu
2+
stoichiometry
A
= cl
1.86E04
1.82E04
2.80E03
1.05E03
Wash effect
Retention of bisligand Cu
2+

sites after extensive washing
with pH 4.2 buffered saline

Ligand only hrdrogel
50 mM Cu
2+
treated
n hydrogel
Washed hydrogel
Dosimeter for ultratrace concentration of Cu
2+

Sense > 1M Cu
2+
Response of washed Cu
2+
cross-linked 8-
hydroxyquinoline PCCACS
Two runs showing reproducible and
reversible nature of the sensor response
to Cu
2+

Reversible sensor for > 1M Cu
2+
cross-
linked
Nonspecific metal cation sensor

K
1
=10
9.57
K
3
=10
18.27
K
1
=10
10.70
K
3
=10
21.87
Cu
2+
Ni
2+

Nonspecific metal cation sensor

Co
2+
Zn
2+

air
N
2

N
2
: K
1
=10
8.11
K
3
=10
15.05
Oxidation Co
2+
Co
3+

K
1
=10
8.65
K
3
=10
16.15
Conclusions
Novel sensing material is formed to evaluate
metal concentrations in drinking water.
Metal cation concentrations can be
determined visually from the color of the
diffracted light or detected by reflectance
measurements using a spectrophotometer.

Conclusions
At low metal concentrations bisligand
complexes form crosslink the gelshrink
blue shift observed

At higher metal concentrations monoligand
complexes form cross-links break red shift
observed

Conclusions
At trace concentration (10
-21
M), used as
dosimeters; at low concentration (> 1M),
used as reversible sensor
Detects metal cations such as Cu
2+
,
Ni
2+
,Co
2+
, Co
3+
, Ca
2+
, Zn
2+
AND other cation
such as Th
4+
,Sm
3+
, Fe
3+
, Gd
3+
, and Er
3+

which has similar 8-hydroxyquinoline
association constants

Design and Synthesis of Novel
Quinoline-based Contrast
Agents for Diagnostic Imaging

Kendra D. Salter and Mark D. Kernen

The University of Tennessee at Martin
Developments in lanthanide coordination chemistry: Smart CA platforms
Compounds such as the gadolinium tetraamide complex above have proven
to be effective at catalyzing the rate of relaxation of bulk water protons
in their hydration spheres, making them excellent MRI contrast agents
when given in doses of 2 to 3 g per patient.

Dual sensing smart probes for specific analytes that allow for both
luminescent and MR imaging (use of Eu/Tb and Gd) can serve to
revolutionize MR-based neuroimaging techniques.
Design and Synthesis of Novel Quinoline-based Contrast
Tissue imaging has
been performed using
lanthanide complexes
alone or in conjunction with
selective dyes.
Pandya, S; Yu, J. and Parker, D. Dalton Trans. 2006, 2757.
Eu-complex RNA-select dye co-localization
Design principles: Luminescent lanthanide sensors and sensitized emission
Complex without target analyte
In the presence of analyte, coordination
sphere and energy transfer changes
result in significant changes in either the
optical signal (or MRI signal, depending on the
lanthanide chosen).
Developments in luminescent lanthanide complexes: Next-generation sensor platforms
The DO3A cyclen is frequently applied in
the synthesis of lanthanide complexes,
and has a history of use in early and modern
MRI contrast agents.

Similarly, the DO3AM triamide can also be
employed as a complexing platform.
Our work on lanthanide complexes: quinoline-cyclen dual sensor synthesis.
O-substituted quinoline linker syntheses:
Our work on lanthanide complexes: quinoline-based dual-mode CA synthesis.
Coupling to cyclen and completion of the complex:
Our work on lanthanide complexes: quinoline-based dual sensor synthesis.
Coupling to cyclen and completion of the complex:
Flow Injection Analysis
Flow Injection Analysis (FIA)
In FIA, a sample is injected into a moving liquid stream to which various reagents can be
added. After suitable time, the reacted sample reaches a spectrophotometric cell detector.
(Left) Schematic diagram of FIA, showing two different reagent addition schemes.
(Right) FIA system with enlarged view of chemistry section.
A dialysis flow module.
The membrane is supported
between two grooved Teflon
blocks.
FIA apparatus for the determination of caffeine
in acetylsalicylic acid preparation.
FIA of ppb levels of H
2
O
2
in air.

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